KR20230034160A - Organopolysiloxane Composition - Google Patents

Abstract

The objective of the present invention is to provide an organopolysiloxane composition that dissolves in an aprotic solvent and, when used as a silane coupling agent or fiber treatment agent, suppresses the generation of alcohol while also improving compatibility with hydrophobic organic materials and hydrophobic inorganic materials, wherein the composition is uniform and transparent and has amino and silanol groups. The transparent organopolysiloxane composition contains only a powdery silicone resin represented by general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent. In the formula, R^1 each independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a hetero atom, R^2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and "a" represents an integer from 2 to 70.

Description

Organopolysiloxane composition

The present invention relates to organopolysiloxane compositions.

An organosilicon compound having a hydrolyzable silyl group and an organic group is usually used because a silanol group generated by hydrolysis of a hydrolyzable silyl group forms a covalent bond with a hydroxyl group on the surface of an inorganic material and the organic group reacts with the organic material. It makes it possible to bond organic materials and inorganic materials that are difficult to bond with. As a result, properties such as heat resistance, water resistance, weather resistance, improvement in mechanical strength, adhesion, dispersibility, hydrophobicity, and rust prevention can be imparted to the organic-inorganic composite material.

Using these properties, the organosilicon compound is used in a wide range of fields and applications, such as silane coupling agents, resin additives, surface treatment agents, fiber treatment agents, adhesives, paint additives, and polymer modifiers.

Among the organosilicon compounds, the aminosilane compound having an amino group can improve the adhesion of the organic-inorganic composite material because the amino group shows high reactivity with various organic and inorganic materials.

As such an aminosilane compound, 3-aminopropyltrimethoxysilane (patent document 1) is mentioned, for example. Moreover, as an organopolysiloxane composition obtained by hydrolyzing this aminosilane compound, 3-aminopropylsilane triol homopolymer (patent document 2) is mentioned, for example.

Japanese Unexamined Patent Publication No. Hei 10-17578 Specification of US Patent Application Publication No. 2020/0068897

However, in the aminosilane compound having an alkoxysilyl group described in Patent Literature 1, a significant amount of alcohol is generated by hydrolysis of the alkoxysilyl group. In recent years, in environmental problems closely related to global warming and health problems, reduction of volatile organic compounds (VOCs) has been cited as a major theme, and the aminosilane compounds generate a large amount of alcohol, which causes a load on the environment. I am concerned.

In this respect, the organopolysiloxane composition having an amino group and a silanol group described in Patent Document 2 is a silanol condensate produced by hydrolyzing an aminosilane compound having an alkoxysilyl group, and the alcohol generated after hydrolysis can be removed. Therefore, it is useful as one of the methods for reducing the amount of alcohol produced by the aminosilane compound.

In addition, since this organopolysiloxane composition is a silanol condensate having a plurality of silanol groups, it also has an advantage of having excellent reactivity with respect to hydroxyl groups on the surface of the substrate. That is, in the hydrolysis reaction of the aminosilane compound, silanol condensates having linear, branched, cyclic or three-dimensional network structures are produced by condensation of silanol groups. Since the condensation of silanol groups reaches equilibrium by the interaction of a silanol group and an amino group, a plurality of silanol groups exist in a state in which no condensation occurs in the silanol condensate. As a result, since a plurality of silanol groups can react with a plurality of hydroxyl groups on the surface of the substrate, adhesion to the organic-inorganic composite material is improved.

However, although the organopolysiloxane composition described in Patent Document 2 having an amino group and a silanol group can remove generated alcohol, since the solvent exhibiting compatibility is limited to protonic solvents such as water or lower alcohol, it is aprotic. When a solvent is used, a uniform and transparent solution cannot be prepared. That is, since the silanol condensate contained in the organopolysiloxane composition is derived from a plurality of silanol groups and exhibits hydrophilicity, a solid (crystalline product) or liquid (oil product) having low compatibility with an aprotic solvent. is precipitated or separated as In the case of a non-uniform and opaque solution containing these solids or liquids, since it cannot sufficiently contact various organic materials and inorganic materials, the reactivity with hydroxyl groups on the surface of the substrate is reduced. In addition, in the case of a solution containing a protic solvent such as water or a lower alcohol, compatibility with hydrophobic organic materials and hydrophobic inorganic materials is low, so it was not applicable in the use of blending them.

Therefore, it has solubility in aprotic solvents and can improve compatibility with hydrophobic organic materials and hydrophobic inorganic materials while suppressing the generation of alcohol when used as a silane coupling agent or fiber treatment agent. It is desired to develop an organopolysiloxane composition having an amino group and a silanol group and transparent.

The present invention was made in view of the above circumstances, and when dissolved in an aprotic solvent and used as a silane coupling agent or a fiber treatment agent, while suppressing the generation of alcohol, compatibility with hydrophobic organic materials and hydrophobic inorganic materials It is an object of the present invention to provide a uniform, transparent, organopolysiloxane composition having an amino group and a silanol group that can improve

As a result of repeated intensive studies in order to achieve the above object, the inventors of the present invention have found that a powdery silicone resin having an amino group and a silanol group dissolves in an aprotic solvent by interaction with a carboxylic acid compound. To form a uniform and transparent solution (composition) that does not cause precipitation or liquid separation, and when this composition is used as a silane coupling agent or fiber treatment agent, alcohol is not generated, and hydrophobic organic materials and hydrophobic inorganic materials It was found that compatibility with materials was improved, and the invention was completed.

That is, the present invention

1. A transparent organopolysiloxane composition containing only a powdery silicone resin represented by the following general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent,

(Wherein, R ¹ each independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and R ² each independently represents a hydrogen atom, a methyl group or an ethyl group and a represents an integer from 2 to 70.)

2. The organopolysiloxane composition of 1 above, wherein the average particle diameter of the silicone resin as determined by dry laser diffraction is 1 to 200 µm in volume-based median diameter;

3. The organopolysiloxane composition of 1 or 2, wherein the silicone resin is spray-dried particles;

4. Any one of 1 to 3 organopolysiloxane compositions wherein the carboxylic acid compound is one or two or more selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic acids having 3 to 22 carbon atoms ,

5. The organopolysiloxane composition of any one of 1 to 4, wherein the aprotic solvent is one or two or more selected from saturated aliphatic hydrocarbon-based solvents, unsaturated aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, and ketone-based solvents.

provides

The organopolysiloxane composition of the present invention can be prepared as a uniform and transparent solution in which solid precipitation or liquid separation does not occur.

In addition, since the organopolysiloxane composition of the present invention exhibits high compatibility with hydrophobic organic materials and hydrophobic inorganic materials, when used as a silane coupling agent or a fiber treatment agent, adhesion to organic-inorganic composite materials can be improved. there is.

Hereinafter, the present invention will be described in detail.

The organopolysiloxane composition of the present invention is a powdery silicone resin represented by the following general formula (1) (hereinafter referred to as “silicone resin (1)”), a carboxylic acid compound or a natural carboxylic acid compound-containing compound. It contains only oils and aprotic solvents.

In the general formula (1), R ¹ is each independently a substituted or unsubstituted group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which may contain a hetero atom. Represents a divalent hydrocarbon group.

The divalent hydrocarbon group for R ¹ may be linear, branched or cyclic, and specific examples thereof include methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, and nona. Linear alkyls such as methylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, and icosamethylene groups Rengi; isopropylene, isobutylene, sec-butylene, tert-butylene, isopentylene, isohexylene, isoheptylene, isooctylene, isononylene, isodecylene, isundecylene, isododecylene, isotri branched chain alkylene groups such as decylene, isotetradecylene, isopentadecylene, isohexadecylene, isoheptadecylene, isooctadecylene, isononadecylene, and isoicosylene groups; Cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene, cyclotridecylene, cyclotetradecylene, cyclo Cyclic alkylene groups, such as pentadecylene, cyclohexadecylene, cycloheptadecylene, cyclooctadecylene, cyclononadecylene, and cycloicoxylene; Ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentade alkenylene groups such as cenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene, and icocenylene groups; arylene groups such as phenylene and naphthylene groups; Aralkylene groups, such as a methylene phenylene and a methylene phenylene methylene group, are mentioned. Examples of the divalent hydrocarbon group containing a hetero atom for R ¹ include an alkyleneaminoalkylene group, an alkyleneoxyalkylene group, an alkylenethioalkylene group, and the like, and examples of these alkylene groups are each independently the above linear chain. , groups similar to the groups exemplified for the branched-chain and cyclic alkylene groups are exemplified.

In addition, some or all of the hydrogen atoms of these divalent hydrocarbon groups may be substituted with other substituents, and specific examples of these substituents include carbon atoms of 1 to 4, such as methoxy, ethoxy, and (iso)propoxy groups. alkoxy group; halogen atoms such as fluorine, chlorine and bromine; aryl groups such as phenyl, tolyl, and xylyl groups; aralkyl groups such as benzyl and phenethyl groups; A cyano group, an amino group, an ester group, an ether group, a carbonyl group, an acyl group, a sulfide group, etc. may be mentioned, and one type or a combination of two or more types may be used among these. Substitution positions of these substituents are not particularly limited, and the number of substituents is also not limited.

Among these, examples of R ¹ include an unsubstituted, straight-chain, branched-chain or cyclic alkylene group having 1 to 8 carbon atoms; alkenylene group; arylene group; Aralkylene group; Alkyleneaminoalkylene group; Alkyleneoxyalkylene group; An alkylenethioalkylene group is preferable, and particularly, from the viewpoint of availability of precursor raw materials, unsubstituted, straight-chain or branched-chain alkylene groups having 1 to 6 carbon atoms; An alkyleneaminoalkylene group is more preferable, and a methylene group, a dimethylene group, a trimethylene group, an isopropylene group, a methyleneaminomethylene group, a methyleneaminodimethylene group, a methyleneaminotrimethylene group, a dimethyleneaminomethylene group, and a dimethylene group. An aminodimethylene group, a dimethyleneaminotrimethylene group, a trimethyleneaminomethylene group, a trimethyleneaminodimethylene group, and a trimethyleneaminotrimethylene group are more preferable.

In the general formula (1), R ² each independently represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom from the viewpoint of availability of precursor raw materials.

In the general formula (1), a is an integer of 2 to 70, but is preferably 2 to 60, more preferably 2 to 50, and still more preferably 2, especially from the viewpoint of compatibility with aprotic solvents. to 40, more preferably 5 to 40, still more preferably 15 to 40, and particularly preferably 20 to 40.

In addition, the range of a in General formula (1) can be known by measuring the amine value of silicone resin (1). Here, the amine value is a value representing the amount of organic amine in the sample, and is calculated by measuring mg of potassium hydroxide (KOH) equivalent to an acid required to neutralize the amino group of the organic amine contained in 1 g of the sample by potentiometric titration. .

Specific examples of the silicone resin (1) include 1-aminomethylsilanetriol homopolymer, 2-aminoethylsilanetriol homopolymer, 2-aminoisopropylsilanetriol homopolymer, and 3-aminopropylsilanetriol homopolymer. A silicone resin having a primary amino group of; N-methyl-1-aminomethylsilanetriol homopolymer, N-methyl-2-aminoethylsilanetriol homopolymer, N-methyl-2-aminoisopropylsilanetriol homopolymer, N-methyl-3-amino silicone resins having secondary amino groups such as propylsilanetriol homopolymer; N,N-dimethyl-1-aminomethylsilanetriol homopolymer, N,N-dimethyl-2-aminoethylsilanetriol homopolymer, N,N-dimethyl-2-aminoisopropylsilanetriol homopolymer, N , Silicone resin having a tertiary amino group such as N-dimethyl-3-aminopropylsilanetriol homopolymer; N-(1-aminomethyl)-1-aminomethylsilanetriol homopolymer, N-(1-aminomethyl)-2-aminoethylsilanetriol homopolymer, N-(1-aminomethyl)-2-amino Isopropylsilanetriol Homopolymer, N-(1-aminomethyl)-3-aminopropylsilanetriol Homopolymer, N-(2-aminoethyl)-1-aminomethylsilanetriol Homopolymer, N-(2 -Aminoethyl)-2-aminoethylsilanetriol homopolymer, N-(2-aminoethyl)-2-aminoisopropylsilanetriol homopolymer, N-(2-aminoethyl)-3-aminopropylsilanetriol Ol Homopolymer, N-(2-aminoisopropyl)-1-aminomethylsilanetriol Homopolymer, N-(2-aminoisopropyl)-2-aminoethylsilanetriol Homopolymer, N-(2-amino Isopropyl)-2-aminoisopropylsilanetriol homopolymer, N-(2-aminoisopropyl)-3-aminopropylsilanetriol homopolymer, N-(3-aminopropyl)-1-aminomethylsilanetriol Ol Homopolymer, N-(3-aminopropyl)-2-aminoethylsilanetriol Homopolymer, N-(3-aminopropyl)-2-aminoisopropylsilanetriol Homopolymer, N-(3-aminopropyl) )-3-aminopropylsilanetriol homopolymer and the like, and silicone resins having diamino groups.

Among these, especially when used as a silane coupling agent or a fiber treatment agent, 1-aminomethylsilanetriol homopolymer, 2-aminoethylsilanetriol, from the viewpoint of reacting with a plurality of hydroxyl groups on the surface of the substrate to improve adhesion to organic materials ol homopolymer, 2-aminoisopropylsilanetriol homopolymer, 3-aminopropylsilanetriol homopolymer, N-(1-aminomethyl)-1-aminomethylsilanetriol homopolymer, N-(1-amino Methyl)-2-aminoethylsilanetriol homopolymer, N-(1-aminomethyl)-2-aminoisopropylsilanetriol homopolymer, N-(1-aminomethyl)-3-aminopropylsilanetriol homopolymer Polymer, N-(2-aminoethyl)-1-aminomethylsilanetriol homopolymer, N-(2-aminoethyl)-2-aminoethylsilanetriol homopolymer, N-(2-aminoethyl)-2 -Aminoisopropylsilanetriol homopolymer, N-(2-aminoethyl)-3-aminopropylsilanetriol homopolymer, N-(2-aminoisopropyl)-1-aminomethylsilanetriol homopolymer, N -(2-aminoisopropyl)-2-aminoethylsilanetriol homopolymer, N-(2-aminoisopropyl)-2-aminoisopropylsilanetriol homopolymer, N-(2-aminoisopropyl)- 3-aminopropylsilanetriol homopolymer, N-(3-aminopropyl)-1-aminomethylsilanetriol homopolymer, N-(3-aminopropyl)-2-aminoethylsilanetriol homopolymer, N- (3-aminopropyl)-2-aminoisopropylsilanetriol homopolymer and N-(3-aminopropyl)-3-aminopropylsilanetriol homopolymer are preferred.

The silicone resin 1 used in the present invention is a powdery solid.

The particle shape of the silicone resin 1 may be any shape such as spherical shape, polyhedral shape, spindle shape, needle shape, or plate shape, but spherical shape is preferable from the viewpoint of ease of handling. In addition, in the present invention, spherical means that the shape of the particles does not mean only a spherical shape, but also includes an ellipsoid. In addition, the shape of the particle is confirmed by observing the particle with an optical microscope, an electron microscope or the like.

The average particle diameter of the silicone resin 1 is preferably 1 to 200 μm, more preferably 10 to 150 μm, still more preferably 30 to 100 μm, from the viewpoint of promoting interaction with the carboxylic acid compound. am.

In addition, an average particle diameter means the volume-based median diameter (D50) measured by the dry laser diffraction method. The volume-based median diameter was determined by the Fraunhofer diffraction theory using a laser diffraction type particle size distribution analyzer Mastersizer 3000 (manufactured by Malvern) by a dry method under conditions of a dispersion pressure of 2 bar and a scattering intensity of 2 to 10% on a volume basis. It is calculated by measuring the diameter corresponding to the 50% cumulative value of the cumulative particle size distribution curve of .

The coarse bulk density of the silicone resin (1) is preferably 0.2 to 0.9 g/mL, more preferably 0.25 to 0.9 g/mL, still more preferably from the viewpoint of promoting interaction with the carboxylic acid compound. is from 0.3 to 0.9 g/mL.

In addition, for the bulk density, put the powdery silicone resin into a 100 ml container whose mass has been measured in advance until it overflows (at this time, do not apply vibration to the measuring container or compress the sample), and rise from the upper end surface of the container. It calculates by measuring the mass of a net weight, and calculating the mass per 1 mL by milling a powder using a milling pan.

The silicone resin (1) is usually produced by hydrolyzing an aminosilane compound having an alkoxysilyl group represented by the following general formula (2).

In the general formula (2), examples of R ¹ and R ² are the same as those of the substituents exemplified above. Each R ³ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms.

The monovalent hydrocarbon group for R ³ may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, linear alkyl groups such as n-octyl, n-nonyl, and n-decyl groups; sec-propyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert-hexyl, sec-heptyl, tert-heptyl, sec-octyl, tert-octyl, sec-nonyl, tert- branched chain alkyl groups such as nonyl, sec-decyl, and tert-decyl groups; Cyclic alkyl groups, such as a cyclopentyl and a cyclohexyl group; alkenyl groups such as vinyl, allyl, butenyl, and methallyl groups; aryl groups such as phenyl, tolyl, and xylyl groups; Aralkyl groups, such as a benzyl and a phenethyl group, etc. are mentioned.

In addition, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with other substituents, and as a specific example of this substituent, some or all of the hydrogen atoms of the divalent hydrocarbon group of R ¹ may be substituted with other substituents. The same substituents as the substituents in the case where they may be substituted are exemplified, and among these, one type or a combination of two or more types may be used. Substitution positions of these substituents are not particularly limited, and the number of substituents is also not limited.

Among these, as R ³ , an unsubstituted straight-chain alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable, particularly from the viewpoint of availability.

As specific examples of the aminosilane compound having an alkoxysilyl group, 1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-amino trialkoxysilane compounds having a primary amino group such as isopropyltrimethoxysilane, 2-aminoisopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; N-methyl-1-aminomethyltrimethoxysilane, N-methyl-1-aminomethyltriethoxysilane, N-methyl-2-aminoethyltrimethoxysilane, N-methyl-2-aminoethyltriethoxy Silane, N-methyl-2-aminoisopropyltrimethoxysilane, N-methyl-2-aminoisopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-amino trialkoxysilane compounds having secondary amino groups such as propyltriethoxysilane; N,N-dimethyl-1-aminomethyltrimethoxysilane, N,N-dimethyl-1-aminomethyltriethoxysilane, N,N-dimethyl-2-aminoethyltrimethoxysilane, N,N-dimethyl -2-aminoethyltriethoxysilane, N,N-dimethyl-2-aminoisopropyltrimethoxysilane, N,N-dimethyl-2-aminoisopropyltriethoxysilane, N,N-dimethyl-3- trialkoxysilane compounds having tertiary amino groups such as aminopropyltrimethoxysilane and N,N-dimethyl-3-aminopropyltriethoxysilane; N-(1-aminomethyl)-1-aminomethyltrimethoxysilane, N-(1-aminomethyl)-1-aminomethyltriethoxysilane, N-(1-aminomethyl)-2-aminoethyltri Methoxysilane, N-(1-aminomethyl)-2-aminoethyltriethoxysilane, N-(1-aminomethyl)-2-aminoisopropyltrimethoxysilane, N-(1-aminomethyl)- 2-aminoisopropyltriethoxysilane, N-(1-aminomethyl)-3-aminopropyltrimethoxysilane, N-(1-aminomethyl)-3-aminopropyltriethoxysilane, N-(2 -Aminoethyl)-1-aminomethyltrimethoxysilane, N-(2-aminoethyl)-1-aminomethyltriethoxysilane, N-(2-aminoethyl)-2-aminoethyltrimethoxysilane, N-(2-aminoethyl)-2-aminoethyltriethoxysilane, N-(2-aminoethyl)-2-aminoisopropyltrimethoxysilane, N-(2-aminoethyl)-2-aminoiso Propyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoisopropyl )-1-aminomethyltrimethoxysilane, N-(2-aminoisopropyl)-1-aminomethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoethyltrimethoxysilane, N -(2-aminoisopropyl)-2-aminoethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyltrimethoxysilane, N-(2-aminoisopropyl)-2- Aminoisopropyltriethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltrimethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltriethoxysilane, N-(3 -Aminopropyl)-1-aminomethyltrimethoxysilane, N-(3-aminopropyl)-1-aminomethyltriethoxysilane, N-(3-aminopropyl)-2-aminoethyltrimethoxysilane, N-(3-aminopropyl)-2-aminoethyltriethoxysilane, N-(3-aminopropyl)-2-aminoisopropyltrimethoxysilane, N-(3-aminopropyl)-2-aminoiso Trialkoxysilanes having a diamino group such as propyltriethoxysilane, N-(3-aminopropyl)-3-aminopropyltrimethoxysilane, and N-(3-aminopropyl)-3-aminopropyltriethoxysilane A compound etc. are mentioned.

Among these, especially when used as a silane coupling agent or a fiber treatment agent, 1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane from the viewpoint of reacting with a plurality of hydroxyl groups on the surface of a substrate to improve adhesion to organic materials Silane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoisopropyltrimethoxysilane, 2-aminoisopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-(1-aminomethyl)-1-aminomethyltrimethoxysilane, N-(1-aminomethyl)-1-aminomethyltriethoxysilane, N-(1-amino Methyl)-2-aminoethyltrimethoxysilane, N-(1-aminomethyl)-2-aminoethyltriethoxysilane, N-(1-aminomethyl)-2-aminoisopropyltrimethoxysilane, N -(1-aminomethyl)-2-aminoisopropyltriethoxysilane, N-(1-aminomethyl)-3-aminopropyltrimethoxysilane, N-(1-aminomethyl)-3-aminopropyltri Ethoxysilane, N-(2-aminoethyl)-1-aminomethyltrimethoxysilane, N-(2-aminoethyl)-1-aminomethyltriethoxysilane, N-(2-aminoethyl)-2 -Aminoethyltrimethoxysilane, N-(2-aminoethyl)-2-aminoethyltriethoxysilane, N-(2-aminoethyl)-2-aminoisopropyltrimethoxysilane, N-(2- Aminoethyl)-2-aminoisopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoisopropyl)-1-aminomethyltrimethoxysilane, N-(2-aminoisopropyl)-1-aminomethyltriethoxysilane, N-(2-aminoisopropyl)-2- Aminoethyltrimethoxysilane, N-(2-aminoisopropyl)-2-aminoethyltriethoxysilane, N-(2-aminoisopropyl)-2-aminoisopropyltrimethoxysilane, N-(2 -Aminoisopropyl)-2-aminoisopropyltriethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltrimethoxysilane, N-(2-aminoisopropyl)-3-aminopropyltri Ethoxysilane, N-(3-aminopropyl)-1-aminomethyltrimethoxysilane, N-(3-aminopropyl)-1-aminomethyltriethoxysilane, N-( 3-aminopropyl)-2-aminoethyltrimethoxysilane, N-(3-aminopropyl)-2-aminoethyltriethoxysilane, N-(3-aminopropyl)-2-aminoisopropyltrimethoxy Silane, N-(3-aminopropyl)-2-aminoisopropyltriethoxysilane, N-(3-aminopropyl)-3-aminopropyltrimethoxysilane, N-(3-aminopropyl)-3- Aminopropyltriethoxysilane is preferred.

In hydrolysis of an aminosilane compound having an alkoxysilyl group, a considerable amount of alcohol is generated corresponding to the alkoxysilyl group. In addition, depending on the amount of water used for hydrolysis, water may be included.

As described above, since the organopolysiloxane composition of the present invention is a uniform and transparent solution in which the silicone resin (1) is dissolved in an aprotic solvent, from the viewpoint of compatibility with the aprotic solvent, the silicone resin (1) It is preferable to remove alcohol and water from the silver hydrolysis liquid.

The method for removing alcohol and water from the hydrolysis liquid is not particularly limited, and removal methods such as centrifugation, heat drying, chromatography, recrystallization, distillation, extraction, decantation, liquid separation, and filtration can be employed. Among these, heat drying is preferable from a viewpoint of productivity.

In addition, as specific examples of the method for producing a powdery silicone resin, a method of heating and pulverizing a still hydrolyzed liquid, a method of heating and stirring a hydrolyzed liquid, a method of stirring and flowing a hydrolyzed liquid, spraying a hydrolyzed liquid into a high-temperature air stream such as a spray dryer, A spray drying method for dispersing (spray drying method), a method using a fluid heat medium, and the like are exemplified.

The spray drying method is a granulation method in which a solution containing a solid and a solvent is decomposed (sprayed) into small droplets, brought into contact with a high-temperature air stream in a drying chamber to evaporate the solvent instantaneously, to obtain a powdery solid (particles).

The driving force for evaporating the solvent is generally obtained by making the partial pressure of the solvent lower than the vapor pressure of the solvent at the temperature at which the droplets are dried. Preferred embodiments include a method of mixing liquid droplets with a high-temperature dry gas, a method of maintaining the pressure in the solvent removal device at an incomplete vacuum, and the like.

The solution can be sprayed into the drying chamber over a wide range of flow rates and temperatures. Further, in the case of applying pressure at the time of spraying, it is possible to spray in a wide range of pressures. In general, the evaporation rate of the solvent increases with the increase in the specific surface area of the droplet.

For this reason, the diameter of the droplets to be sprayed is preferably less than 500 μm, more preferably less than 400 μm, and still more preferably 5 to 200 μm. In addition, flow rates, temperatures, and pressures that allow such atomization are preferred.

The solution supply flow rate is preferably 1 to 500 kg/h, more preferably 5 to 100 kg/h, still more preferably 10 to 50 kg/h.

The inlet temperature of the drying chamber is preferably 100 to 250°C, more preferably 110 to 220°C, still more preferably 120 to 200°C.

The temperature at the outlet of the drying chamber is preferably 0 to 100°C, more preferably 0 to 95°C, still more preferably 0 to 90°C.

The solution supply pressure is preferably 100 to 50,000 kPa, more preferably 200 to 10,000 kPa, still more preferably 300 to 5,000 kPa.

As a method for producing powdery silicone resin, when a method of heating and pulverizing a still standing hydrolyzate using a vacuum dryer or the like is adopted, solvent and moisture remain, so when used as a silane coupling agent or fiber treatment agent, Adhesion to the organic-inorganic composite material is lowered.

On the other hand, in the spray drying method, since the specific surface area of the sprayed particles is extremely large, the solvent and moisture are efficiently evaporated and removed. As a result, since the content of the solvent and moisture is lower than that of powdering by other methods, the powdery silicone resin produced by the spray drying method has an advantage of excellent adhesion to the organic-inorganic composite material. Therefore, from the viewpoint of controlling the content of solvent and moisture, and controlling physical properties such as average particle size and bulk density, the silicone resin used in the present invention is preferably spray-dried particles obtained by a spray drying method.

The content of the silicone resin (1) in the organopolysiloxane composition is not particularly limited as long as it reacts with a plurality of hydroxyl groups on the surface of the substrate to increase adhesion when used as a silane coupling agent or a fiber treatment agent, but from the viewpoint of productivity , With respect to the organopolysiloxane composition, it is preferably 0.001 to 99% by mass, more preferably 0.01 to 50% by mass, still more preferably 0.1 to 10% by mass.

The carboxylic acid compound used in the organopolysiloxane composition of the present invention is not particularly limited, but is selected from saturated monocarboxylic acid compounds having 1 to 11 carbon atoms and unsaturated monocarboxylic acids having 3 to 22 carbon atoms, or 2 or more types are preferable.

Specific examples thereof include saturated monocarboxylic acid compounds having 1 to 11 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, and undecylic acid; Acrylic acid, methacrylic acid, isocrotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, myristoleic acid, pentadecenoic acid, Hexadecenoic Acid, Hexadecadienoic Acid, Hexadecatrienoic Acid, Hexadecatetraenoic Acid, Palmitoleic Acid, Sapienic Acid, Heptadecenoic Acid, Heptadecadienoic Acid, Heptadecatrienoic Acid, Heptadecatetraenoic Acid, Octadecanoic Acid Decenoic acid, octadecadienoic acid, octadecatrienoic acid, octadecatetraenoic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecenoic acid, nonadecadienoic acid, nonadecatrienoic acid, nonadeca Tetraenoic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, gadoleic acid, arachidonic acid, docosenoic acid, docosadienoic acid, docosatienoic acid, unsaturated monocarboxylic acid compounds having 3 to 22 carbon atoms, such as docosatetraenoic acid, docosahexaenoic acid, and erucic acid; these carboxylic acid compounds may be used singly; You may mix more than a species.

Moreover, you may use the natural oil containing these carboxylic acid compounds for the organopolysiloxane composition of this invention.

Specific examples of natural oils include almond oil, Astrocarium Murumuru seed butter, avocado oil, horseradish seed oil, linseed oil, Argania spinosa kernel oil, apricot kernel oil, olive fruit oil, cacao butter, dog rose fruit oil, Canola Oil, Alpine Oil, Kukui Nut Oil, Blackcurrant Seed Oil, Corn Oil, Sesame Oil, Wheat Germ Oil, Rice Bran Oil, Rice Germ Oil, Pomegranate Seed Oil, Safflower Oil, Shea Butter, Sclerocarya Vireya Seed Oil, Soybean Oil, Tea Seed Oil, Evening Primrose Oil, Camellia Seed Oil, Theobroma Grandiflorum Seed Butter, Palm Kernel Oil, Palm Kernel Oil, Palm Oil, Horse Oil, Hybrid Safflower Oil, Hybrid Sunflower Oil, Peanut Oil, Pistachio Seed Oil, Castor Oil, Sunflower Seed Oil, Grape Seed Oil, Hazelnut Seed oil, jojoba seed oil, macadamia seed oil, mango seed oil, meadowfoam oil, Japan wax, peach kernel oil, palm fatty acid, palm oil, peanut oil, borage seed oil, rosehip oil, moringa seed oil and the like.

Among these, especially from the viewpoint of availability, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, acrylic acid, methacrylic acid, isocrotone Acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, myristoleic acid, pentadecenoic acid, hexadecenoic acid, hexadecenoic acid , Hexadecatrienoic acid, hexadecatetraenoic acid, palmitoleic acid, sapienoic acid, heptadenoic acid, heptadecadienoic acid, heptadecatrienoic acid, heptadecatetraenoic acid, octadecenoic acid, octadecadienoic acid, Octadecatrienoic acid, octadecatetraenoic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecenoic acid, nonadecadienoic acid, nonadecatrienoic acid, nonadecatetraenoic acid, eicosenoic acid, eico Sadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, gadoleic acid, arachidonic acid, docosenic acid, docosadienoic acid, docosatienoic acid, docosatetraenoic acid, docosa Hexaenoic acid and erucic acid are preferred, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidonic acid, eico Sapentaenoic acid and docosahexaenoic acid are more preferred.

The carboxylic acid compound interacts with the silicone resin (1). Specifically, while the carboxyl group of the carboxylic acid compound reacts with the amino group of the silicone resin 1 to form a salt or amide bond, it also reacts with a silanol group to form an ester bond. Since the hydrophobicity of the silicone resin 1 formed with a salt, amide bond or ester bond is improved by the hydrocarbon group of the carboxylic acid compound, compatibility with an aprotic solvent is improved.

As described above, since the organopolysiloxane composition of the present invention is a uniform and transparent solution in which the silicone resin 1 is dissolved in an aprotic solvent, from the viewpoint of compatibility with the aprotic solvent, the carboxylic acid compound is , It is preferable to use a monocarboxylic acid compound that does not form a cross-linked structure. Further, from the viewpoint of accelerating the interaction with the silicone resin 1, it is preferable to use a liquid monocarboxylic acid compound compatible with an aprotic solvent.

The content of the carboxylic acid compound in the organopolysiloxane composition is not particularly limited as long as the organopolysiloxane composition is a uniform and transparent solution, but from the viewpoint of productivity, the organopolysiloxane composition is preferably 0.001 to 99 % by mass, more preferably 0.01 to 50% by mass, still more preferably 0.1 to 10% by mass.

Specific examples of the aprotic solvent used in the organopolysiloxane composition of the present invention include pentane, isopentane, cyclopentane, hexane, isohexane, cyclohexane, heptane, isoheptane, octane, isooctane, nonane, isononane, decane, Saturated aliphatics such as isodecane, dodecane, isododecane, tetradecane, isotetradecane, hexadecane, isohexadecane, octadecane, isooctadecane, eicosane, isoeicosane, liquid paraffin, liquid isoparaffin, and squalane hydrocarbon-based solvents; Unsaturated aliphatic hydrocarbon-based solvents such as pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, and squalene ; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, mesitylene, styrene, and tetralin; ketone solvents such as acetone and methyl isobutyl ketone; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile and N,N-dimethylformamide; Chlorinated hydrocarbon solvents, such as dichloromethane and chloroform, etc. are mentioned, These solvents may be used individually by 1 type, and may mix 2 or more types.

Among these, especially from the viewpoint of compatibility with hydrophobic organic materials and hydrophobic inorganic materials, one or two or more selected from saturated aliphatic hydrocarbon-based solvents, unsaturated aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents and ketone-based solvents It is preferred, and one or two or more selected from saturated aliphatic hydrocarbon-based solvents and aromatic hydrocarbon-based solvents are more preferred.

The content of the aprotic solvent in the organopolysiloxane composition is not particularly limited as long as the organopolysiloxane composition is a uniform and transparent solution, but from the viewpoint of productivity, the organopolysiloxane composition is preferably 1 to 99 It is mass %, More preferably, it is 10-90 mass %, Even more preferably, it is 20-80 mass %.

The organopolysiloxane composition of the present invention contains only a silicone resin (1), a carboxylic acid compound or a natural oil containing the same, and an aprotic solvent, and is a uniform and transparent solution in which solid precipitation or liquid separation does not occur. form

The method for producing the organopolysiloxane composition is not particularly limited as long as the silicone resin (1) is dissolved in an aprotic solvent, and the silicone resin (1) is added to a solution containing a carboxylic acid compound and an aprotic solvent. method, a method of adding a solution containing silicone resin (1) and a carboxylic acid compound to an aprotic solvent, a method of adding a solution containing silicone resin (1) and an aprotic solvent to a carboxylic acid compound, A method of adding a carboxylic acid compound to a solution containing a silicone resin (1) and an aprotic solvent, a method of adding a solution containing a carboxylic acid compound and an aprotic solvent to a silicone resin (1), and an aprotic solvent Any of a method of adding an acidic solvent to a solution containing the silicone resin 1 and a carboxylic acid compound and a method of simultaneously mixing the silicone resin 1 with a carboxylic acid compound and an aprotic solvent may be used, but the productivity From this point of view, a method of simultaneously mixing the silicone resin 1, a carboxylic acid compound, and an aprotic solvent is preferable.

From the viewpoint of productivity, the mixing temperature is preferably 20 to 100°C, more preferably 20 to 60°C, still more preferably 20 to 40°C.

The mixing time is, from the viewpoint of productivity, preferably 1 to 72 hours, more preferably 1 to 48 hours, still more preferably 1 to 24 hours, but it may be appropriately set in relation to the above preparation temperature. .

As described above, the organopolysiloxane composition of the present invention is a uniform and transparent composition containing three components: a silicone resin (1), a carboxylic acid compound or natural oil containing the same, and an aprotic solvent. The polysiloxane composition can be used for various applications by adding other additives.

In this case, the composition to which other additives are added may be uniform and transparent, similar to the organopolysiloxane composition of the present invention, or may become non-uniform and opaque as a result of adding other additives, resulting in solid precipitation or liquid separation. may occur

Other additives include solid, semi-solid or liquid emulsions, water, alcohols, water-soluble polymers, film formers, surfactants, oil-soluble gelling agents, organic modified clay minerals, powders, sweat inhibitors, and ultraviolet absorbers used in common cosmetics. , UV absorbing and scattering agents, moisturizers, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, ingredients for skin care (whitening agents, cell activators, skin roughness improving agents, blood circulation promoters, skin astringents) , anti-seborrhea agents, etc.), vitamins, amino acids, nucleic acids, hormones, clathrate compounds, solidifying agents for hair, and the like.

Although the specific example of an additive is given below, this invention is not limited by these.

Examples of solid, semi-solid or liquid oils include hydrocarbon oils, higher alcohols, ester oils, glyceride oils, silicone oils, and fluorine-based oils.

Examples of hydrocarbon oil include ozokerite, α-olefin oligomer, light isoparaffin, isododecane, isohexadecane, light liquid isoparaffin, squalane, synthetic squalane, vegetable squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, Polyethylene/polypropylene wax, (ethylene/propylene/styrene) copolymer, (butylene/propylene/styrene) copolymer, liquid paraffin, liquid isoparaffin, pristane, polyisobutylene, hydrogenated polyisobutene, microcrystal Lean wax, petroleum jelly, etc. are mentioned.

As the higher alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl Alcohol, 2-decyl tetradecinol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (selachyl alcohol), etc. are mentioned.

Ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, and trimethylolpropane triisostearate. , Ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane of tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleic acid Oleyl, octyldodecyl oleate, decyl oleate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, stearic acid Butyl, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isononanoate isononanoate, isotridecyl isononanoate, isopropyl palmitate, 2-ethyl palmitate Hexyl, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearyl acid, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristic acid, myristyl myristate, hexyldecyl dimethyl octanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, lauroyl Sarcosine isopropyl ester, diisostearyl malate, etc. are mentioned.

Examples of the glyceride oil include acetic glyceryl, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tribehenate, glyceryl monostearate, and glyceryl di-2-heptylundecanoate , trimyristate glyceryl, myristic acid isostearic acid diglyceryl, etc. are mentioned.

As the silicone oil, dimethylpolysiloxane, tritrimethylsiloxymethylsilane, caprylylmethicone, phenyltrimethicone, tetrakistrimethylsiloxysilane, methylphenylpolysiloxane, methylhexylpolysiloxane, methylhydrogenpolysiloxane, dimethylsiloxane/methylphenylsiloxane copolymer low to high viscosity straight-chain or branched organopolysiloxanes such as; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogen cyclotetrasiloxane, and tetramethyltetraphenylcyclotetrasiloxane; Amino-modified organopolysiloxane, pyrrolidone-modified organopolysiloxane, pyrrolidone carboxylic acid-modified organopolysiloxane, high polymerization degree gummy dimethylpolysiloxane, gummy amino-modified organopolysiloxane, gummy dimethylsiloxane/methylphenylsiloxane copolymer, etc. solutions of silicone rubbers and cyclic organopolysiloxanes of silicone gums or rubbers; higher alkoxy-modified silicones such as stearoxysilicone; Higher fatty acid-modified silicone, alkyl-modified silicone, long-chain alkyl-modified silicone, amino acid-modified silicone, fluorine-modified silicone, and the like.

Examples of the fluorine-based emulsion include perfluoropolyether, perfluorodecalin, and perfluorooctane.

Examples of alcohols include lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol and maltose; sterols such as cholesterol, sitosterol, phytosterol, and lanosterol; polyhydric alcohols such as butylene glycol, propylene glycol, dibutylene glycol, and pentylene glycol; and the like.

Examples of water-soluble polymers include gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat, etc.), plant-based polymers such as algae colloid, trant gum, and locust bean gum; microbial polymers such as xanthan gum, dextran, succinoglucan, and pullulan; animal-based polymers such as collagen, casein, albumin, and gelatin; starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose-based polymers of cellulose end; alginic acid-based polymers such as sodium alginate and alginate propylene glycol ester; vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymer; acrylic polymers such as polyoxyethylene-based polymers, polyoxyethylene-polyoxypropylene copolymer-based polymers, sodium polyacrylate, polyethyl acrylate, polyacrylamide, and acryloyldimethyltaurine salt copolymers; other synthetic water-soluble polymers such as polyethyleneimine and cationic polymers; and inorganic water-soluble polymers such as bentonite, aluminum magnesium silicate, montmorillonite, beidelite, nontronite, saponite, hectorite, and silicic anhydride.

Examples of the film forming agent include latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and alkyl polyacrylate; Cellulose derivatives, such as a dextrin, an alkyl cellulose, and nitrocellulose; siliconized polysaccharide compounds such as tri(trimethylsiloxy)silylpropylcarbamate pullulan; acrylic-silicone-based graft copolymers such as (alkyl acrylate/dimethicone) copolymers; silicone resins such as trimethylsiloxysilicic acid; silicone-based resins such as silicone-modified polynorbornene and fluorine-modified silicone resin; Fluorine resins, aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutene, polyisoprene, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, polyurethanes, and the like.

Examples of the surfactant include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and their salts, condensate salts of amino acids and fatty acids, alkanesulfonates, alkenesulfonates, sulfonates of fatty acid esters, and fatty acid amides. sulfonic acid salts, formalin condensed sulfonic acid salts, alkyl sulfate ester salts, higher secondary alcohol sulfate ester salts, alkyl and allyl ether sulfate ester salts, sulfuric acid ester salts of fatty acid esters, sulfuric acid ester salts of fatty acid alkylolamides, lot oil anionic surfactants such as sulfate ester salts, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates, amide phosphates, N-acyl lactates, N-acyl sarcosine salts, and N-acyl amino acid-based activators; amine salts such as alkylamine salts, polyamines and aminoalcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridinium salts, and cationic surfactants such as imidazolium salts; Sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, methyl glucoside fatty acid ester, alkyl polyglucoside, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether , polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, Polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, linear or branched polyoxyalkylene modified organopolysiloxane , linear or branched polyoxyalkylene/alkyl co-modified organopolysiloxanes, linear or branched polyglycerin-modified organopolysiloxanes, linear or branched polyglycerin/alkyl co-modified organopolysiloxanes, alkanolamides, nonionic surfactants such as sugar ethers and sugar amides; amphoteric surfactants such as betaine, phosphatidylcholine, aminocarboxylic acid salts, imidazoline derivatives, and amide amine types; and the like.

Examples of the oil-soluble gelling agent include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin fatty acid esters such as dextrin palmitic acid ester, dextrin stearic acid ester, and dextrin 2-ethylhexanoic acid palmitic acid ester; sucrose fatty acid esters such as sucrose palmitic acid ester and sucrose stearic acid ester; fructooligosaccharide fatty acid esters such as fructooligosaccharide stearic acid ester and fructooligosaccharide 2-ethylhexanoic acid ester; and benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol.

Examples of organic modified clay minerals include dimethylbenzyldodecylammonium montmorillonite clay, dimethyldioctadecylammonium montmorillonite clay and the like.

Examples of the powder include those used in normal cosmetics, regardless of its shape (spherical, needle-like, plate-like, etc.), particle size (aerosol, fine particles, pigment grade, etc.) and particle structure (porous, non-porous, etc.) , Any of them can be used, and examples thereof include powders selected from inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigments, tar colorants, and natural pigments.

Examples of the inorganic powder include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite mica, synthetic mica, and phlogopite mica. , Lonite mica, biotite, lithian mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, higilite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dibasic calcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica and the like.

As the organic powder, polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, Cellulose, silk powder, nylon powder, nylon 12, nylon 6, silicone powder, styrene/acrylic acid copolymer, divinylbenzene/styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine Resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine, etc. are mentioned.

As the surfactant metal salt powder (metal soap), zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, etc. can be heard

As the colored pigment, inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as iron sulfate and ocher, inorganic black pigments such as black iron oxide and carbon black, manganese violet, Inorganic purple pigments such as cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate, inorganic blue pigments such as Prussian blue and ultramarine blue, tar pigments laked, and natural pigments laked synthetic resin powder obtained by compounding these powders; and the like.

Examples of pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish meal, and titanium oxide-coated colored mica.

As a metal powder pigment, aluminum powder, copper powder, stainless steel powder, etc. are mentioned.

As tar pigment, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230 No., Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, and the like.

As a natural pigment, carminic acid, laccaic acid, cartamine, brasilin, crocin, etc. are mentioned.

As these powders, those obtained by combining powders or those treated with common oils, silicone oils, fluorine compounds, surfactants, etc. can also be used, and those treated with a hydrolysable silyl group or an alkyl group having a hydrogen atom directly bonded to a silicon atom can be used. Straight-chain and/or branched organopolysiloxanes having decomposable silyl groups or hydrogen atoms directly bonded to silicon atoms, linear and/or branched organopolysiloxanes having hydrolysable silyl groups or hydrogen atoms directly bonded to silicon atoms and co-modified with long-chain alkyls. Organopolysiloxane, straight-chain and/or branched organopolysiloxane having hydrolysable silyl groups or hydrogen atoms directly bonded to silicon atoms and co-modified with polyoxyalkylene, acrylics having hydrolyzable silyl groups or hydrogen atoms directly bonded to silicon atoms. -Silicone-based copolymers can also be used singly or in combination as needed.

As an antiperspirant, aluminum chlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum zirconium hydroxychloride, aluminum zirconium glycine complex, etc. are mentioned.

Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid; anthranilic acid-based ultraviolet absorbers such as methyl anthranilate; salicylic acid-based ultraviolet absorbers such as methyl salicylate, octyl salicylate, and trimethylcyclohexyl salicylate; cinnamic acid-based ultraviolet absorbers such as octyl paramethoxycinnamate; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone; urocanic acid-based ultraviolet absorbers such as ethyl urocanate; dibenzoylmethane-based ultraviolet absorbers such as 4-t-butyl-4'-methoxy-dibenzoylmethane; Phenylbenzimidazole sulfonic acid, triazine derivatives, etc. are mentioned.

Examples of the ultraviolet absorbing and scattering agent include powders that absorb and scatter ultraviolet rays, such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof. Dispersed dispersions can also be used.

As a humectant, glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, egg yolk lecithin, soybean lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipids and the like.

Examples of preservatives and antibacterial agents include paraoxybenzoic acid alkyl esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, phenolic acid, parachloromethacresol, and hexachlorophene. , benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, butylcarbamate propynyl iodide, polylysine, photosensitizer, silver, plant extracts and the like.

As the fragrance, natural fragrance and synthetic fragrance are exemplified.

Examples of natural flavors include vegetable flavors separated from flowers, leaves, ashes, fruit skins, and the like, and animal flavors such as musk and civet.

Examples of the synthetic fragrance include hydrocarbons such as monoterpenes; alcohols such as aliphatic alcohols and aromatic alcohols; aldehydes such as terpene aldehyde and aromatic aldehyde; ketones such as alicyclic ketones; esters such as terpene esters; Lactones, phenols, oxides, nitrogen-containing compounds, acetals, etc. are mentioned.

Examples of salts include inorganic salts, organic acid salts, amine salts, and amino acid salts.

Examples of inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid.

Examples of organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid.

Examples of amine salts and amino acid salts include salts of amines such as triethanolamine and amino acids such as glutamic acid. In addition, salts of hyaluronic acid, chondroitin sulfate, and the like, and furthermore, acid-alkali neutralized salts used during preparation of pharmaceutical preparations, and the like can also be used.

Examples of antioxidants include carotenoids, ascorbic acid and salts thereof, ascorbyl stearate, tocophenol, tocophenol acetate, tocopherol, p-t-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfite, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, kaempferol, myricetin, quercetin and the like.

As a pH adjuster, potassium carbonate, sodium hydrogencarbonate, ammonium hydrogencarbonate, etc. are mentioned.

Examples of the chelating agent include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid.

Examples of the cooling agent include L-menthol, camphor, and menthyl lactate.

Examples of the anti-inflammatory agent include allantoin, glycyrrhizic acid and salts thereof, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, and azulene.

Examples of components for skin care include whitening agents such as placenta extract, arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizer, cholesterol derivatives, and calf blood extract; Skin roughening agent, vanillinamide nonylic acid, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantharis tincture, ichtamol, caffeine, tannic acid, α-borneol, nicotinic acid tocopherol, inositolhexanicotyl blood circulation promoters such as nate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharantin, and γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrhea agents such as sulfur and thianthol. can

As vitamins, vitamin A oil, retinol, retinol acetate, vitamin A, such as retinol palmitate, vitamin B2, such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmi Vitamin B6 such as tate, vitamin B12 and its derivatives, vitamin B15 and its derivatives, L-ascorbic acid, L-ascorbic acid dipalmitic acid ester, L-ascorbic acid-2-sulfate, L-ascorb Vitamin C such as dipotassium acid phosphate diester dipotassium, vitamin D such as ergocalciferol and cholecalciferol, α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α- nicotinic acid Vitamin E such as tocopherol and dl-α-tocopherol succinate, nicotinic acid such as nicotinic acid, benzyl nicotinate, and nicotinic acid amide, vitamin H, vitamin P, calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, and acetyl pantothenyl ethyl Pantothenic acids, such as ether, biotin, etc. are mentioned.

Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan.

As a nucleic acid, deoxyribonucleic acid etc. are mentioned.

As a hormone, estradiol, ethenyl estradiol, etc. are mentioned.

As a clathrate compound, cyclodextrin etc. are mentioned.

Examples of the solidifying agent for hair include amphoteric, anionic, cationic, and nonionic polymer compounds, polyvinylpyrrolidone-based polymer compounds such as polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymer, methyl Acidic vinyl ether-based polymer compounds such as vinyl ether/alkyl maleic anhydride half ester copolymers, acidic polyvinyl acetate-based polymers such as vinyl acetate/crotonic acid copolymers, (meth)acrylic acid/alkyl (meth)acrylate copolymers, Acidic acrylic high molecular compounds such as (meth)acrylic acid/alkyl (meth)acrylate/alkylacrylamide copolymers, N-methacryloylethyl-N, N-dimethylammonium/α-N-methylcarboxybetaine/alkyl ( and amphoteric acrylic high molecular compounds such as meth)acrylate copolymers and hydroxypropyl (meth)acrylate/butylaminoethyl methacrylate/octylamide acrylic acid copolymers. In addition, naturally occurring high molecular compounds such as cellulose or derivatives thereof, keratin and collagen or derivatives thereof can also be suitably used.

The adhesion of the organic-inorganic composite material after the treatment can be improved by performing the silane coupling treatment or the fiber treatment of the base material using the organopolysiloxane composition of the present invention. Below, the treatment method of the base material using the organopolysiloxane composition of this invention is demonstrated.

The method for treating a substrate using the organopolysiloxane composition of the present invention is not particularly limited, and the organopolysiloxane composition is applied to a substrate, the organopolysiloxane composition is entrained in an inert gas, and the substrate is entrained in the entrained gas. and a method of directly mixing the organopolysiloxane composition with a base material with a mixer or mill. Among these, the method of applying an organopolysiloxane composition from a viewpoint of simplicity is preferable.

Examples of the method for applying the organopolysiloxane composition include a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method, and a dipping method.

Conditions for applying, contacting or mixing the organopolysiloxane composition of the present invention to a substrate are not particularly limited as long as the silanol groups of the silicone resin 1 react with hydroxyl groups on the surface of the substrate.

From the viewpoint of productivity, the treatment temperature is preferably 0 to 100°C, more preferably 10 to 50°C, and still more preferably 20 to 30°C.

From the viewpoint of productivity, the treatment time is preferably 1 minute to 10 hours, more preferably 1 minute to 5 hours, still more preferably 1 minute to 2 hours, and appropriately in relation to the treatment temperature. Just set it up.

The substrate to be treated may be either an inorganic material or an organic material.

Examples of inorganic materials include silicon compounds such as glass plate, glass fiber, diatomaceous earth, calcium silicate, silica, silicon, talc, and mica; metal oxides such as zinc oxide, aluminum oxide, tin oxide, titanium oxide, iron oxide, and magnesium oxide; metal chlorides such as zinc chloride, aluminum chloride, tin chloride, titanium chloride, iron chloride, and magnesium chloride; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; Carbonates, such as calcium carbonate, zinc carbonate, and magnesium carbonate, etc. are mentioned. Among these, a silicon compound and a metal oxide are especially preferable from a reactive viewpoint with the silanol group of an organopolysiloxane composition.

Examples of organic materials include natural polymers such as rubber, paper, and cellulose; synthetic polymers such as acrylic resins, urethane resins, epoxy resins, and phenol resins; Oils and fats, surfactants, liquid crystals, and the like are exemplified. Among these, natural polymers and synthetic polymers are particularly preferred from the viewpoint of reactivity with amino groups of the organopolysiloxane composition.

After treating a substrate using the organopolysiloxane composition of the present invention, excess organopolysiloxane composition can be removed by a conventional method such as washing or drying. Further, post-treatment by washing and drying may be performed alone or in combination.

[Example]

Hereinafter, the present invention will be described in more detail by way of synthesis examples, examples, comparative examples, and application examples, but the present invention is not limited to the following examples.

In addition, the weight average particle diameter is a volume-based median diameter (D90) measured by a dry laser diffraction method. The volume-based median diameter was determined by the Fraunhofer diffraction theory in a dry method using a laser diffraction type particle size distribution analyzer Mastersizer 3000 (manufactured by Malvern), under the conditions of a dispersion pressure of 2 bar and a scattering intensity of 2 to 10% in a dry method, The diameter corresponding to the 50% cumulative value of the volume-based cumulative particle size distribution curve was measured.

In addition, the interfacial shear strength τ [MPa] of the glass fiber epoxy resin composite material was determined by measuring the diameter of the glass fiber by D [μm] by the microdroplet method using a composite interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.). ], where L [㎛] is the length of the glass fiber embedded in the cured epoxy resin material, and F [mN] is the load when the cured epoxy resin material is drawn in the axial direction of the glass fiber, and τ = F / πDL Calculated by Eq.

[1] Synthesis of powdery silicone resin by spray drying method

[Synthesis Example 1] Synthesis of powdery 3-aminopropylsilanetriol homopolymer

A 30% by mass aqueous solution of 3-aminopropylsilanetriol homopolymer was prepared by spray drying (solution supply flow rate 11 kg/h, drying chamber inlet temperature 140 ° C., drying chamber outlet temperature 85 ° C., solution supply pressure 100 kPa), from the aqueous solution. Water was removed to obtain a powdery 3-aminopropylsilanetriol homopolymer.

By titrating the obtained powdery 3-aminopropylsilanetriol homopolymer by potentiometric titration, it was confirmed that the amine value was 480.7 KOHmg/g. In addition, by measuring by dry laser diffraction method, it was confirmed that the average particle diameter was 40.6 µm and the coarse bulk density was 0.263 g/mL.

[2] Preparation of organopolysiloxane composition

[Example 1]

To 100 parts by mass of toluene as an aprotic solvent, 1 part by mass of the powdery 3-aminopropylsilanetriol homopolymer prepared in Synthesis Example 1 and 10 parts by mass of butyric acid as a carboxylic acid compound were added at room temperature, followed by 24 hours at room temperature Stir. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 2]

Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of isododecane. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 3]

Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of isohexadecane. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 4]

Except having changed the aprotic solvent to 100 mass parts of squalane, it carried out similarly to Example 1, and stirred. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 5]

Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of tetradecene. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 6]

Except having changed the aprotic solvent to 100 mass parts of squalene, it carried out similarly to Example 1, and stirred. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 7]

Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of acetone. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform brown transparent liquid organopolysiloxane composition was obtained.

[Example 8]

Stirring was carried out in the same manner as in Example 1, except that the aprotic solvent was changed to 100 parts by mass of tetrahydrofuran. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 9]

It stirred in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of caproic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 10]

It stirred in the same manner as in Example 1 except that the carboxylic acid compound was changed to 10 parts by mass of caprylic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 11]

Stirring was carried out in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of undecylic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 12]

It stirred in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 13]

It stirred in the same manner as in Example 2, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 14]

It stirred in the same manner as in Example 3, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 15]

It stirred in the same manner as in Example 4, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 16]

It stirred in the same manner as in Example 5, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 17]

It stirred in the same manner as in Example 6, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 18]

It stirred in the same manner as in Example 7, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 19]

It stirred in the same manner as in Example 8, except that the carboxylic acid compound was changed to 10 parts by mass of oleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 20]

It stirred in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of linoleic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Example 21]

It stirred in the same manner as in Example 1, except that the carboxylic acid compound was changed to 10 parts by mass of linolenic acid. During stirring, the 3-aminopropylsilanetriol homopolymer was dissolved, and a uniform pale yellow transparent liquid organopolysiloxane composition was obtained.

[Comparative Example 1]

Although stirring was performed in the same manner as in Example 1 except that the carboxylic acid compound was not used, the 3-aminopropylsilanetriol homopolymer did not dissolve.

[Comparative Example 2]

Example 1, except that 1 part by mass of the powdery 3-aminopropylsilanetriol homopolymer prepared in Synthesis Example 1 was changed to 1 part by mass of the bulky 3-aminopropylsilanetriol homopolymer prepared using a vacuum dryer and a pulverizer. Although stirring was carried out in the same manner as above, the 3-aminopropylsilanetriol homopolymer did not dissolve.

[Application example 1]

[1] Fiber treatment with an organopolysiloxane composition

Glass fibers (length of about 300 mm, diameter of about 23 μm) were immersed in the solution of the organopolysiloxane composition obtained in Example 1 at 25° C. for 30 minutes to perform a fiber treatment, and then the glass fibers were pulled out of the solution and then heated to 70° C. After drying for 2 hours, post-treatment was performed.

[2] Molding of glass fiber epoxy resin composite material

The diameter of the epoxy resin composition composed of the organopolysiloxane-treated glass fiber obtained above, an epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd.: JER828), and a curing agent (manufactured by Tokyo Kasei Kogyo Co., Ltd.: triethylenetetramine) After attaching the droplets so that the droplets do not contact each other, the first step was thermally cured at 80°C for 1.5 hours and the second step was thermally cured at 100°C for 2 hours to mold a glass fiber epoxy resin composite material.

[Application Example 2]

Fiber treatment and composite material were molded in the same manner as in Application Example 1, except that the organopolysiloxane composition was changed to the solution of Example 2.

[Application Example 3]

Fiber treatment and composite material were molded in the same manner as in Application Example 1, except that the organopolysiloxane composition was changed to the solution of Example 12.

[Comparative application example 1]

A glass fiber epoxy resin composite material was molded in the same manner as [2] of Application Example 1 using glass fibers (length of about 300 mm, diameter of about 23 μm) that had not been subjected to fiber treatment with the organopolysiloxane composition.

[Performance evaluation]

Interfacial shear strength was measured by the microdroplet method for the glass fiber epoxy resin composite material molded in Application Examples 1 to 3 and Comparative Application Example 1 using a composite interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.). τ [MPa] was measured. The larger the number, the better the adhesion of the glass fiber epoxy resin composite material. The results are shown in Table 1.

As shown in Table 1, in the glass fiber epoxy resin composite materials obtained in Application Examples 1 to 3, the plurality of silanol groups contained in the powdery silicone resin react with the plurality of hydroxyl groups on the surface of the glass fiber, and the amino group reacts with the epoxy resin. Since it reacts with the resin, it can be seen that the adhesion to the glass fiber epoxy resin composite material is improved.

Claims (5)

A transparent organopolysiloxane composition containing only a powdery silicone resin represented by the following general formula (1), a carboxylic acid compound or a natural oil containing a carboxylic acid compound, and an aprotic solvent.

(Wherein, R ¹ each independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and R ² each independently represents a hydrogen atom, a methyl group or an ethyl group and a represents an integer from 2 to 70.) The organopolysiloxane composition according to claim 1, wherein the average particle diameter of the silicone resin as determined by dry laser diffraction is 1 to 200 µm in terms of volume-based median diameter. The organopolysiloxane composition according to claim 1 or 2, wherein the silicone resin is a spray dry particle. The organo according to claim 1 or 2, wherein the carboxylic acid compound is one or more selected from a saturated monocarboxylic acid compound having 1 to 11 carbon atoms and an unsaturated monocarboxylic acid compound having 3 to 22 carbon atoms. Polysiloxane composition. The organopolysiloxane composition according to claim 1 or 2, wherein the aprotic solvent is one or more selected from saturated aliphatic hydrocarbon-based solvents, unsaturated aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, and ketone-based solvents. .